Silver halide color photographic material

ABSTRACT

A silver halide color photographic material comprising a support having thereon a yellow color forming silver halide emulsion layer, a magenta color forming silver halide emulsion layer and a cyan color forming silver halide emulsion layer. The yellow color forming emulsion layer contains a silver halide emulsion having a silver chloride content of not less than 90 mol %, a yellow coupler and a bisphenol compound and optionally a difficultly water-soluble epoxy compound. One or more layers of the light-sensitive material may contain an ultraviolet light absorber.

FIELD OF THE INVENTION

This invention relates to a multi-layer silver halide color photographicmaterial suitable for use in rapid processing. More particularly, itrelates to a silver halide color photographic material which isexcellent in fastness to light after processing, and still moreparticularly, to a silver halide color photographic material which isexcellent in color developability.

BACKGROUND OF THE INVENTION

There are widely used methods for the color development of exposedlight-sensitive materials with color developing agents, which involvethe incorporation of photographic couplers, i.e., three color couplersof yellow, magenta and cyan couplers, into light-sensitive emulsionlayers to form a color photographic dye.

It is required that the thus-formed developed dyes are bright yellow,magenta and cyan dyes having little secondary absorption and givephotographic color images with good color reproducibility.

On the other hand, it is required that the formed photographic colorimages can be well-preserved under various conditions. Namely, it isrequired that the dye images are prevented to the extent possible fromfading and discoloring and that stain is prevented to the extentpossible from forming even when the color images are exposed to lightover a long period of time and stored under high temperature andhumidity conditions. Further, it is necessary that all three colors areprevented from fading to the same degree. However, there is apossibility that an improved method for preventing the fading of acertain dye image has an adverse effect—the color balance of the threecolors is lost after fading and as a result, the quality of thephotographic image deteriorates thereby.

There are many methods for improving the fastness of magenta dye imagesand cyan dye images at present, and the fastness of the images can becontrolled. However, there is no method for improving the fastness ofyellow dye images to light without having an adverse effect.Accordingly, it is a demand for a new method.

Some attempts have been made to improve the fastness of developed yellowdye images. To improve fastness to light, ultraviolet light absorbers toprotect the dye image from ultraviolet rays and anti-fading agents whichprevent the dye image from being faded by light, have been proposed.

For example, in the method for improving the light resistance of the dyeimage by adding ultraviolet light absorbers to color photographicmaterials, light resistance can be greatly improved in comparison withmethods in which no ultraviolet light absorber is added. However, whenthe ultraviolet light absorbers are used in such an amount as to obtaina sufficient effect, there is the problem that white grounds areyellowed because the ultraviolet light absorbers themselves are colored.Further, when the ultraviolet light absorbers are used, they do not havethe effect of preventing the dye image from being faded by visiblelight, and hence there is a limitation with regard to the degree ofimprovement in light resistance.

Among the anti-fading agents which prevent the dye image from beingfaded by light, there are many compounds which deteriorate thepreservability of the dye image in a dark place, cause staining on whitegrounds or the discoloration of the dye image by light, heat andhumidity or interfere with the color formation of the couplers. Hence, asufficient color density can not be obtained. Accordingly, they havemany practical problems. The bisphenols described in JP-B-48-31256 (theterm “JP-B” as used herein means an “examined Japanese patentpublication”) and JP-B-48-31625 interfere with the color formation ofthe couplers, and hence they have practical problems. Particularly, whensilver halide color photographic materials containing high silverchloride content emulsions having a silver chloride content of not lessthan 90 mol % are subjected to rapid processing with developingsolutions containing no benzyl alcohol, there is the problem that thesebisphenols are apt to lower the color density. Even when the amounts ofthe bisphenols to be added were increased, contrast was lightly loweredand an effect of improving sufficient fastness to light for practicaluse could not be obtained. Further, JP-A-64-50048 (the term “JP-A” asused herein means an “unexamined published Japanese patentapplication”), JP-A-64-50049 and JP-A-61-4041 disclose that cyclic ethercompounds or compounds having an epoxy group are added to thephotographic materials. However, an improving effect obtained hereby isstill insufficient.

For the purposes of recording and storage, the light-sensitive materialsmust have the property that an image obtained immediately afterprocessing not deteriorate even when the image is stored over a longperiod of time. At present, yellow dye images are poor in preservabilityin a dark place and the color thereof is likely to become turbid whenstored over a long period of time. JP-A-64-50048, JP-A-64-50049 andJP-A-61-4041 l disclose the use of cyclic ether compounds or epoxygroup-containing compounds to solve these problems. However, theimprovement obtained thereby is still insufficient sufficient.Particularly, when rapid processing is carried out with developingsolutions containing no benzyl alcohol, the effect obtained thereby islow. A solution to the problem of color turbidity of yellow dye imagescan be scarcely obtained, and there is a demand for a new method.

The present inventors have found that the fastness of yellow dye imagesto light can be greatly improved unexpectedly by using certainbisphenols in combination with ultraviolet light absorbers. Further, ithas been found that color developability can be greatly improved byusing certain epoxy compounds in combination therewith. The presentinvention has been accomplished on the basis of these findings.

SUMMARY OF THE INVENTION

One object of the present invention is to provide a silver halide colorphotographic material in which the fastness of the developed yellowcolor part to light after processing is improved to a sufficient level.

Another object of the present invention is to provide a silver halidecolor photographic material which is excellent in color developabilityand in which the fastness of developed yellow color part to light afterprocessing is improved to a sufficient level.

The above-described objects of the present invention have been achievedby a silver halide color photographic material comprising a supporthaving thereon a yellow color forming silver halide emulsion layer, amagenta color forming silver halide emulsion layer and a cyan colorforming silver halide emulsion layer. The yellow color forming emulsionlayer contains, (i) at least one high silver chloride emulsion having asilver chloride content of not less than 90 mol %, (ii) at least oneyellow coupler represented by the following general formula (I) and(iii) at least one compound represented by the following general formula(II). The photographic material also comprises a layer which contains atleast one ultraviolet light absorber.

In general formula (I), R₁ represents a substituent group; R₂ representsa halogen atom, an alkyl group, an aryl group, an alkoxy group, anaryloxy group, a dialkylamino group, an alkylthio group or an arylthiogroup; R₃ represents a group which can be attached to the benzene ring;X₁ represents a hydrogen atom or a group which can be eliminated by acoupling reaction with the oxidation product of an aromatic primaryamine developing agent; and p represents an integer of 0 to 4 and when pis 2 or greater, the two or more R₃ groups may be the same or different.

In general formula ( II ) , R₄, R₅, R₆ and R₇ each represents an alkylgroup having 4 to 18 carbon atoms and the total number of carbon atomsin R₄, R₅, R₆ and R₇ is not more than 32; X₂ represents a simple bond,oxygen atom, sulfur atom, sulfonyl group or a bonding group representedby the following general formula (B):

In general formula (B), R21 and R22 each represents a hydrogen atom oran alkyl group having 1 to 10 carbon atoms; and n represents an integerof 1 to 3 and when n is 2 or 3, the two or three R21 groups and the twoor three R22 groups may be the same or different.

The yellow color forming emulsion layer in the photographic materialdescribed above may also contain at least one difficultly water-solubleepoxy compound having at least one group represented by the followinggeneral formula (AO):

In general formula (AO), R₈, R₉, R₁₀, R₁₁ and R₁₂ may be the same ordifferent and each represents a hydrogen atom, an alkyl group or an arylgroup; R represents a substituent group; n represents an integer of 0 to4; —Y— represents a bivalent bonding group; —X— represents —O—, —S— or—N(R′)—; R′ represents a hydrogen atom, an acyl group, an alkylsulfonylgroup, an arylsulfonyl group, an aryl group, a heterocyclic group or—C(R₁₃)(R₁₄)(R₁₅); and R₁₃, R₁₄ and R₁₅ may be the same or different andeach represents an alkyl group or a group represented by the followinggeneral formula ( AO-1 ) , and R₁₃ and R₁₄ each may also represent ahydrogen atom.

When n is 2 to 4, the two or more R groups may be the same or different;any two of R₈ to R₁₂, R′ and R or two R groups my combine to form afive-membered to seven-membered ring, provided that when X is —S—, thetotal number of carbon atoms in the compound is not less than 15; when Xis —O— and Y is —SO₂— or phenylene, either n is 1 to 4 or at least oneof R₈ to R₁₂ is an alkyl group or an aryl group; and when X is —O— and Yis —O—CO₂—, the total number of carbon atoms in R₈ to R₁₂ and the Rgroup or groups is not less than 10.

The above objects are also achieved by a silver halide colorphotographic material comprising a support having thereon a yellow colorforming silver halide emulsion layer, a magenta color forming silverhalide emulsion layer and a cyan color forming silver halide emulsionlayer, wherein the yellow color forming silver halide emulsion layercontains (i) at least one high silver chloride emulsion having a silverchloride content of not less than 90 mol %, (ii) at least one yellowcoupler represented by above defined general formula (I), (iii) at leastone epoxy compound which has at least one group represented by abovedefined general formula (AO) and which is difficultly soluble in water,and (iv) at least one compound represented by the following generalformula (IV):

In general formula (IV), R₁, R₂, R₃ and R₄ independently represent ahydrogen atom, an aliphatic group, an aromatic group, an aliphaticoxycarbonyl group, an aromatic oxycarbonyl group or a carbamoyl groupwith the proviso that all of R₁, R₂, R₃ and R₄ are not simultaneously ahydrogen atom; the total number of carbon atoms is 8 to 60; and R₁ andR₂ or R₃ and R₄ may combine to form a five-membered to seven-memberedring.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be illustrated in more detail below.

The yellow couplers of general formula (I) which can be used in thepresent invention will be illustrated in more detail below.

In general formula (I), R₁ is preferably an aryl group, a tert-alkylgroup or a group represented by the following general formula (D). Themost preferred tertalkyl group is a t-butyl group.

In general formula (D), R31 represents a mono-valent substituent groupexcluding a hydrogen atom; and Q represents a non-metallic atomic grouprequired for forming a three-membered to five-membered hydrocarbon grouptogether with C or a non-metallic atomic group required for forming athree-membered to five-membered heterocyclic ring together with C, saidheterocyclic ring having at least one hetero-atom, as a member of thering, selected from the group consisting of N, S, O and P. The ringformed by Q together with C may contain one or more unsaturated bonds inthe ring. Examples of the ring formed by Q together with C includecyclopropane ring, cyclobutane ring, a cyclopentane ring, a cyclopropenering, a cyclobutene ring and a cyclopentene ring. R₃₁ is preferably ahalogen atom, a cyano group, a monovalent group having 1 to b 30 carbonatoms (e.g., an alkyl group, an alkoxy group) or a monovalent grouphaving 6 to 30 carbon atoms (e.g., an aryl group, an aryloxy group).

The term R₂ represents a halogen atom, an alkyl group, an aryl group, analkoxy group, an aryloxy group, a dialkylamino group, an alkylthio groupor an arylthio group. Preferably, R₂ is a chlorine atom, a methyl group,an ethyl group or a methoxy group. R₃ represents a substituent groupwhich is attached to benzene ring. Particularly preferably, R₃ is ahalogen atom, an alkoxy group, an aliphatic or aromatic or acylsubstituted carbonamido group, sulfonamido group, sulfamoyl group orcarboxylic acid ester group.

X₁ represents a hydrogen atom or a group which can be eliminated by acoupling reaction with the oxidation product of an aromatic primaryamine developing agent. Particularly preferably, X₁ is an aryloxy groupor a heterocyclic group which is attached to a coupling active sitethrough nitrogen atom. Details regarding the group which can beeliminated by a coupling reaction with the oxidation product of anaromatic primary amine developing agent are disclosed in U.S. Pat. No.4,622,287, at column 7, line 20 to column 8, line 34, and examples ofsuch the group are recited at columns 37 to 54. The recited examples ofthe group can be used in the present invention as X₁. p represents aninteger of 0 to 4, and when p is 2 or greater, the two or more R₃ groupsmay be the same or different.

The couplers of general formula (I) may be in the form of a dimer or apolymer by combining two or more of them through a bivalent orpolyvalent group.

The yellow couplers of general formula (I) are used in an amount of 0.1to 1.0 mol, preferably 0.1 to 0.5 mol, per mol of silver halide.

Specific examples of X₁, R₃ and the yellow couplers of general formula(I) include, but are not limited to, the following groups and compounds:

Examples of X₁:

TABLE 1 Examples of the compounds of general formula (I)

No. R₁ R₂ R₃)p X₁ Y-1 (t)C₄H₉— —OCH₃ (32)* [5]**  (4)* Y-2 (t)C₄H₉——OCH₃ (32) [5]  (5) Y-3 (t)C₄H₉— —CH₃ (31) [5]  (2) Y-4 (t)C₄H₉—

(32) [5]  (5) Y-5 (t)C₄H₉—

(32) [5]  (4) Y-6 (t)C₄H₉— —OCH₃ (33) [5]  (8) Y-7 (t)C₄H₉— —OC₂H₅ (33)[5]  (7) Y-8 (t)C₄H₉— —OCH₃ (31) [5] (23) Y-9 (t)C₄H₉—

(40) [5] (19) Y-10 (t)C₄H₉— —OC₈H₁₇(n) (45) [4]  (5) Y-11 (t)C₄H₉——OC₈H₁₇(n) (45) [5]  (5) Y-12 (t)C₄H₉— —OCH₃ (42) [5]  (4) Y-13 (t)C₄H₉—

(30) [5] (10) Y-14 (t)C₄H₉— —OC₁₆H₃₃(n) — (15) Y-15 (t)C₄H₉——OCH₂CH₂OCH₃ (34) [5]  (8) Y-16 (t)C₄H₉— —CH₃ (43) [5]  (9) Y-17(t)C₄H₉— —C₂H₅ (47) [5]  (8) Y-18 (t)C₄H₉— —OCH₃ (46) [5]  (2) Y-19(t)C₄H₉— —OC₈H₁₇(n) (45) [4]  (5) Y-20 (t)C₄H₉— —OCH₃ (31) [5] (19) (45)[5] Y-21 (t)C₄H₉—

(36) [4] (18) Y-22 (t)C₄H₉—

(41) [5] (11) Y-23 (t)C₄H₉—

(37) [5]  (3) Y-24 (t)C₄H₉— —OC₂H₅ (37) [5]  (1) Y-25 (t)C₄H₉— —CH₃ (38)[5]  (2) Y-26 (t)C₄H₉— —C₂H₅ (38) [5]  (2) Y-27 (t)C₄H₉— —CH₃ (33) [5] (2) Y-28

—OCH₃ (42) [5]  (4) Y-29

(40) [5]  (4) Y-30

—CH₃ (43) [5]  (2) Y-31 (t)C₄H₉— Cl (32) [5]  (4) Y-32 (t)C₄H₉— Cl (42)[5]  (4) Y-33 (t)C₄H₉— Cl (31) [5] (26) Y-34 (t)C₄H₉— Cl (32) [5]  (5)Y-35 (t)C₄H₉— Cl (31) [5] (11) Y-36 (t)C₄H₉— Cl (31) [5] (23) Y-37(t)C₄H₉— Cl (33) [5]  (2) Y-38 (t)C₄H₉— Cl (33) [5]  (7) Y-39

Cl (32) [5]  (4) Y-40

Cl (32) [5]  (4) Y-41

—OCH₃ (37) [5]  (3) Y-42

Cl (32) [5]  (4) Y-43

Cl (31) [5]  (4) Y-44

Cl (32) [5]  (4) Y-45

Cl (42) [5]  (4) *represents the number of the above-described group.**The bracketed part represents the position of the group.

The compounds of general formula (II) are illustrated in more detailbelow.

In general formula (II), X₂ is preferably an alkylene group which may beany of a straight-chain group, a branched-chain group and a cyclicgroup. R₄ to R₇ each represents an alkyl group. The total number ofcarbon atoms in R₄ to R₇ is not more than 32. The term “an alkyl group”encompasses a substituted alkyl group and an unsubstituted alkyl group.The alkyl group may be a straight-chain group, a branched-chain group ora cyclic group. The alkyl groups adjacent to the phenolic hydroxylgroups are preferably secondary or primary alkyl groups.

The compounds of general formula (II) are used in an amount of generally1 to 100 mol %, preferably 1 to 30 mol %, based on the amount of thecoupler of the present invention.

The compounds of general formula (II) can be synthesized in accordancewith the method described in U.S. Pat. No. 3,265,506.

Specific examples of the compounds of general formula (II) include, butare not limited to, the following compounds:

The epoxy compounds having a group represented by general formula (AO)which are difficultly soluble in water according to the presentinvention are illustrated in more detail below.

The epoxy compounds which are difficultly soluble in water refer toepoxy compounds having solubility of not more than 10% in water andhaving not less than 9 carbon atoms, preferably not less than 18 carbonatoms, more preferably not less than 30 carbon atoms, in total.

The “alkyl group” in general formula (AO) is a straight-chain, branchedor cyclic alkyl group (e.g., methyl, ethyl n-propyl, i-propyl, n-butyl,t-butyl, cyclohexyl, n-octyl, t-octyl, n-decyl, sec-dodecyl,n-hexadecyl, n-octadecyl) which may be substituted.

The “aryl group” in general formula (AO) is aromatic hydrocarbon group(e.g., phenyl, naphthyl) which may be substituted.

The “heterocyclic group” in general formula (AO) is a five-membered toseven-membered cyclic group having at least one hetero-atom, as a memberof the ring, selected from the group consisting of an oxygen atom, anitrogen atom and a sulfur atom. The cyclic group may be an aromaticring and may be substituted. Examples of the heterocyclic group includethienyl furyl, imid azolyl, pyrazolyl, pyrrolyl, indolyl, pyridyl,chromanyl, pyrazolidinyl, piperazinyl, 4-morpholinyl and triazinyl.

Examples of the “substituent group” in general formula (AO) include analkyl group, an alkenyl group, an alkinyl group, an aryl group, aheterocyclic group, an alkoxy group, an aryloxy group, an alkylthiogroup, an arylthio group, a hydroxyl group, a halogen atom, a cyanogroup, a nitro group, an acyl group, an acyloxy group, a silyloxy group,a sulfonyl group, a sulfonyloxy group, an alkoxycarbonyl group, anaryloxycarbonyl group, an amido group, an imido group, a carbamoylgroup, a sulfamoyl group, a ureido group, a urethane group, anaminosulfamoyl group, an amino group, an alkylamino group, an arylaminogroup and a heterocyclic amino group.

R₈, R₉, R₁₀, R₁₁, and R₁₂, may be the same or different and eachrepresents a hydrogen atom, an alkyl group or an aryl group; Rrepresents a substituent group; n represents an integer of 0 to 4, andwhen n is 2 to 4, the two or more R groups may be the same or different;—Y— represents a bivalent bonding group (e.g., a simple bond, —O—, —S—,—SO₂—, an imino group which may be substituted with —S—, —O—CO₂—, analkylene group which may be substituted, a phenylene group which may besubstituted, a naphthylene group which may be substituted, a bivalentheterocyclic group); X represents —O—, —S— or —N(R′)—; R′ represents ahydrogen atom, an acyl group (e.g., acetyl, acryloyl, benzoyl), analkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl,dodecanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl,toluenesulfonyl), an aryl group, a heterocyclic group or—C(R₁₃)(R₁₄)(R₁₅); and R₁₃, R₁₄ and R₁₅ may be the same or different andeach represents the above-described alkyl group or a group representedby general formula (AO-1), and R₁₃ and R₁₄ each represents furtherhydrogen atom.

R₈, R₉ and R₁₀ in general formula (AO-1) have the same meaning as ingeneral formula (AO).

Any two of R₈ to R₁₂, R′ and the one R or two R groups may combine toform a five-membered to seven-membered ring, provided that when X is—S—, the total number of carbon atoms in the compound is not less than15; when X is —O— and —Y— is —SO₂— or a phenylene group, either n is aninteger of 1 to 4 or at least one of R₈ to R₁₂ is an alkyl group or anaryl group; or when X is —O— and Y is —O—CO₂—, the total number ofcarbon atoms in R₈ to R₁₂ and the R group or groups is not less than 10.

The atom to which the group represented by general formula (AO) isattached (i.e., through the “—Y—” group) may be a hydrogen atom, acarbon atom, a nitrogen atom, a sulfur atom or an oxygen atom.

Among the epoxy compounds having groups of general formula (AO), thosecompounds having at least three groups, more preferably at least fourgroups, still more preferably at least five groups, of general formula(AO) are preferred from the viewpoint of the benefits of the presentinvention. With regard to the number of benzene rings in the epoxycompounds having groups of general formula (AO), the total number ofbenzene rings is preferably at least two, more preferably at leastthree, still more preferably at least four.

Among the epoxy compounds having groups of general formula (AO),compounds represented by the following general formulas (AE-1), (AE-2),(AE-3) and (AE-4) are preferred:

In general formulas (AE-1) to (AE-3), E represents a group representedby the following general formula (AO-2):

R₈ to R₁₂ and X in general formula (AO-2) have the same meaning as ingeneral formula (AO).

In general formulas (AE-1) to (AE-4), R is as defined above in generalformula (AO); and L₁, L₂ and L₃ may be the same or different and eachrepresents a bivalent bonding group. L₁, L₂ and L₃ are preferably eachan alkylene group which may be substituted. Examples of L₁, L₂ and L₃include the following groups:

In general formulas (AE-1) to (AE--4), n₁ represents an integer of 3 to6; m₁ represents an integer of to 3; n₂ represents an integer of 1 to 5;n₃ represents an integer of 1 to 4; n₄ represents an integer of 1 to 5;m₂ represents an integer of 0 to 4; m₃ represents an integer of 0 to 3;m₄ represents an integer of 0 to 4; n₅ represents an integer of 1 to 5;m₅ represents an integer of 0 to 4; m₆ to m₉ each represents an integerof 0 to 4; p₁ and x each represents a real number of 0 to 20; p₂represents an integer of 3 to 4; and A represents a trivalent ortetravalent organic group. Examples of A include the following groups:

When two or more E or R groups are present, the two or more E groups maybe the same or different, and the two or more R groups may be the sameor different.

The compounds of general formula (AE-2) or (AE-3) may be in the form ofa mixture composed of compounds wherein the number represented by p₁ orp₂ is different.

Among the compounds of general formulas (AE-1) to (AE-4), the compoundsof general formulas (AE-1) to (AE-3) are preferred. More preferred arethe compounds of general formulas (AE-2) to (AE-3). Most preferred arethe compounds of general formula (AE-2).

Among the compounds of general formula (AE-2), compounds wherein —X— ingeneral formula (AO-2) is —O— are preferred. In general formula (AE-2),p₁ is a number of preferably 1 to 20, more preferably 2 to 20, stillmore preferably 3 to 20, most preferably 4 to 20, n₂ to n₄ are eachpreferably a number of 1 to 2, m₂ to m₄ are each preferably a number of0 to 3, most preferably 1 to 2, and R is preferably an alkyl group, ahalogen atom or an alkoxy group.

Specific examples of the compounds of the present invention include, butare not limited to, the following compounds:

Variables x and y in the structural formulas each represent a realnumber and each may be any number, so long as each is in the range of 0to 20, and x may not always be an integer. This is because a mixture ofepoxy compounds having different integers are present in a specificmixing ratio, and x represents the mean number thereof. These epoxycompounds may be used either alone or in combination of two or more.

The epoxy compounds alone according to the present invention or togetherwith couplers may be emulsified and dispersed in a hydrophilic bindersuch as an aqueous gelatin solution by using a surfactant.

The epoxy compounds themselves according to the present invention may beused as high-boiling organic solvents, but the epoxy compounds of thepresent invention may be used together with other high-boiling organicsolvents which have a boiling point of not lower than 160° C. and aredifficultly soluble in water, or with low-boiling organic co-solventsand/or polymers which are insoluble in water, but soluble in organicsolvents. Preferred examples of the high-boiling organic solvents andthe polymers are described in JP-A-64-537. The couplers and thedifficultly water-soluble epoxy compounds may be added to separatelayers, but it is preferred that they are added to the same layer,particularly in the same oil droplets.

The epoxy compounds of the present invention can be obtained, forexample, by reacting bisphenol A with epichlorohydrin in the presence ofsodium hydroxide (see, Plastic Material Lecture, (5) Epoxy Resin, byNaoshiro Oishi, published by Nikkan Kogyo Shinbunsha (Japan)). The epoxycompounds of the present invention are used in an amount of preferably 3to 100% by weight, more preferably 5 to 30% by weight, based on theamount of the yellow coupler.

Any compound having an absorption peak in the range of 330 to 400 nm andno absorption peak in the range of 420 to 750 nm can be used as theultraviolet light absorber of the present invention. However, compoundsrepresented by the following general formula [Va] or [Vb] are preferred:

In general formula [Va], R₁₃ to R₁₆ each represents a hydrogen atom, ahalogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxygroup, an aryl group, an aryloxy group, an acylamino group, a carbamoylgroup, a sulfo group, an alkylthio group or an arylthio group; or R₁₃and R₁₄, and/or R₁₅ and R₁₆ may combine to form a ring.

In general formula [Vb], R₁₇ and R₁₈ each represents a hydrogen atom, analkyl group or an acyl group; X₃ represents —CO— or —COO—; and mrepresents an integer of 3 to 5, n represents an integer of 1 to 4 and prepresents an integer of 1 to 4.

Each group in general formula [Va] or [Vb] may be further substituted.

The number of carbon atoms in each group in general formula [Va] or [Vb]is preferably in the range of 1 to 20.

2-(2′-Hydroxyphenyl)benztriazole ultraviolet light absorbers of generalformula [Va] which can be used in the present invention may be any ofthe compounds which are solid or liquid at room temperature. Examples ofliquid compounds are described in JP-B-55-36984, JP-B-55-12587 andJP-A-58-214152.

The details regarding the atoms or groups represented by R₁₃ to R₁₆ inthe ultraviolet light absorbers of general formula [Va] are described inJP-A-58-221844, JP-A-59-46646, JP-A-59-109055, JP-B-36-10466,JP-B-42-26187, JP-B-48-5496, JP-B-48-41572, U.S. Pat Nos. 3,754,919 and4,220,711.

The details regarding the groups represented by R₁₇ and R₁₈ in thebenzophenone ultraviolet light absorbers of general formula [Vb] aredescribed in JP-B-48-30493 (U.S. Pat. No. 3,698,907) and JP-B-48-31255.

Specific examples of the ultraviolet light absorbers which can be usedin the present invention include, but are not limited to, the followingcompounds:

TABLE 2 Compounds of general formula [Va] No. R_(c) R_(a) R_(b)

V-1  H H —C₄H₉(t) V-2  H H —C₁₂H₂₅(n) V-3  H H —CH₂CH₂COOC₈H₁₇ V-4  Cl H—C₅H₁₁(t) V-5  Cl H —CH₂CH₂COOC₈H₁₇ V-6  H —C₄H₉(sec) —C₄H₉(t) V-7  H—C₅H₁₁(t) —C₅H₁₁(t) V-8  H —C₄H₉(t) —CH₂CH₂COOC₈H₁₇ V-9  H —CH₃ —C₄H₉(t)V-10 Cl —C₄H₉(t) —C₄H₉(t) V-11 Cl —C₄H₉(sec) —C₄H₉(t) V-12 Cl —C₄H₉(t)—CH₂CH₂COOC₈H₁₇ V-13 —OCH₃ —C₄H₉(sec) —C₄H₉(t) V-14 —C₄H₉(sec) —C₄H₉(t)—CH₂CH₂COOC₈H₁₇ V-15 —C₆H₅ —C₅H₁₁(t) —C₅H₁₁(t) V-16 H H —C₁₂H₂₅

V-17 H —C₄H₉(t) —C₄H₉(t) V-18 H H —CH₂CH₂COOC₈H₁₇ V-19 H H —C₁₂H₂₅ V-20Cl —C₄H₉(t) —CH₂CH₂COOC₈H₁₇

TABLE 3 Compounds of general formula [Vb]

No. X₃ R_(a) R_(b) n —(OH) V-21 —CO— 5-OC₄H₉ H 1 V-22 ″ 5-OC₈H₁₇ H 1V-23 ″ 5-OC₁₆H₃₃ H 1 V-24 ″ 5-OC₁₈H₃₇ H 1 V-25 ″ 4-OC₄H₉ 4′-CH₃ 3 2′-,5′- V-26 ″ 5-COCH₃ 3′-C₈H₁₇ 3 2′-, 6′- V-27 ″ 5-C₁₂H₂₅ 4′-OCH₃ 2 2′-,V-28 ″ 5-COCH₃ 3′-C₈H₁₇ 3 2′-, 6′- V-29 ″ 4-OC₁₂H₂₅ 4′-OCH₂C₆H₄-(p)CH₃ 22′- V-30 ″ 5-C₈H₁₇ 4′-COC₆H₄-(p)CH₃ 3 2′-, 6′- V-31 —COO— 4-C₁₂H₂₅4′-C₄H₉(t) 1 V-32 ″ H 4′-C₄H₉(t) 1 V-33 ″ 4-OC₁₂H₂₅ 5′-OCH₃ 2 2′- V-34 ″3-OCH₃ 5′-OC₁₂H₂₅ 2 2′-

In the present invention, the ultraviolet light absorbers may be addedto any layer of the light-sensitive material. Namely, the ultravioletlight absorbers may be added to the emulsion layers, the interlayers,the protective layers or the support. It is particularly preferred thatthe ultraviolet light absorbers are added to the upper silver halideemulsion layer which is the farthest of any emulsion layer from thesupport. It is also preferred that the ultraviolet light absorbers areadded to both the above-described upper silver halide emulsion-layer anda layer above the emulsion layer to stabilize an image.

The ultraviolet light absorbers may be added alone or in combinationwith the high-boiling organic solvents, the water-insoluble polymers andother photographic additives. It is preferred that the ultraviolet lightabsorbers are used in such an amount as to give a transmittance of nothigher than 60%, more preferably not higher than 40%, at 380 nm whencoated on a transparent base.

The compounds of general formula (IV) according to the present inventionare illustrated in more detail below.

In general formula (IV), R₁, R₂, R₃ and R₄ each represents a hydrogenatom, an aliphatic group, an aromatic group, an aliphatic oxycarbonylgroup (e.g., dodecyloxycarbonyl, allyloxycarbonyl), an aromaticoxycarbonyl group (e.g., phenoxycarbonyl) or a carbamoyl group (e.g.,tetradecylcarbamoyl, phenylmethylcarbamoyl) with the proviso that all ofR₁, R₂, R₃ and R₄ are not a hydrogen atom simultaneously. The totalnumber of carbon atoms in R₁ to R₄ is 8 to 60.

The above aliphatic group is a straight-chain, branched or cyclicaliphatic hydrocarbon group including a saturated or unsaturated groupsuch as an alkyl group, an alkenyl group and an alkynyl group. Typicalexamples of the aliphatic group include methyl, ethyl, butyl, dodecyl,octadecyl, eicosenyl, isopropyl, tert-butyl, tert-octyl, tert-dodecyl,cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl and propargyl.

The above aromatic group has preferably 6 to 42 carbon atoms and ispreferably a substituted or unsubstituted phenyl or naphthyl group.

The aliphatic group and the aromatic group stated above may besubstituted by one or more members such as an alkyl group, an arylgroup, a heterocyclic group, an alkoxy group (e.g., methoxy,2-methoxyethoxy), an aryloxy group (e.g., 2,4-di-tert-amylphenoxy,2-chlorophenoxy, 4-cyanophenoxy), an alkenyloxy group (e.g.,2-propenyloxy), an acyl group (e.g., acetyl, benzoyl), an ester group(e.g., butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy,butoxysulfonyl toluenesulfonyloxy), an amido group (e.g., acetylamino,ethyl-carbamoyl, dimethylcarbamoyl, methanesulfonamido, butylsulfamoyl),a sulfamido group (e.g., succinimido, hydantoinyl), a ureido group(e.g., phenylureido, dimethyl-ureido), an aliphatic or aromatic sulfonylgroup (e.g., methanesulfonyl, phenylsulfonyl), an aliphatic or aromaticthio group (e.g., ethylthio, phenylthio) , a hydroxyl group, a cyanogroup, a caboxyl group, a nitro group, a sulfo group and a halogen atom.

Specific examples of the compounds of general formula (IV) include, butare not limited to, the following compounds:

The compounds of general formula (IV) according to the present inventioncan be synthesized by using the method described in Example 1 of U.S.Pat. No. 4,540,657.

The compounds of general formula (IV) alone or together with the epoxycompounds having groups of general formula (AO) and yellow couplers canbe emulsified and dispersed in a hydrophilic binder such as an aqueousgelatin solution by using a surfactant. The compounds of general formula(IV) are used in an amount of preferably 10 to 1000% by weight, morepreferably 100 to 600% by weight, based on the weight of the epoxycompound having groups of general formula (AO).

The term “light-sensitive” or “non-sensitive” is to be understood tomean sensitivity to not only visible light but also to electromagneticwaves in the region of infrared rays. The color photographic material ofthe present invention comprises a support having thereon at least oneyellow color forming a silver halide emulsion layer, at least onemagenta color forming a silver halide emulsion layer and at least onecyan color forming a silver halide emulsion layer.

Generally, these layers are arranged in order of the yellow colorforming silver halide emulsion layer, the magenta color forming silverhalide emulsion layer and the cyan color forming silver halide emulsionlayer, from the support side.

When emulsions sensitive to visible light are used, color reproductionby subtractive color photography can be obtained by including silverhalide emulsions having sensitivity in the region of each wavelength anddyes which have complementary colors to light to be exposed, that is, ayellow coupler to blue, a magenta coupler to green and a cyan coupler tored. However, the relationship between the light-sensitive layer and thehue of the developed color may be different from that described above.

It is preferred that for the purpose of rapid processing that there areused silver halide emulsions comprising silver chloride or silverchlorobromide containing substantially no silver iodide (silver iodidecontent of less than 2 mol %) and having a silver chloride content ofnot less than 90 mol %, more preferably not less than 95 mol %,particularly preferably not less than 98 mol %.

The halogen composition of the emulsion may be different between grains,or grains may have the same halogen composition. However, when emulsionscomprising grains having the same halogen composition are used,photographic performance between grains can be easily made uniform andhence the use of such emulsions is preferred. Further, with regard tohalogen composition distribution in the interiors of the silver halideemulsion grains, there can be used: uniform structure type of grainwherein silver halide grains have the same composition throughout thewhole grain; laminate structure type grains wherein the core in theinterior of silver halide grain is different in halogen composition fromthe shell (single layer or multi-layer) which surrounds the core; andgrains having such a structure in which a different silver compositionexists in a non-laminar form in the interior of the grain or on thesurface thereof (when the part exists on the surface of the grain, thegrain has a structure such that the part having a different halogencomposition is bonded to the edge, corner or plane of the grain). Thesegrains can be properly chosen according to purpose. It is advantageousthat any one of the latter two types rather than the uniform structuretype grain be used to obtain high sensitivity. The latter two types arealso preferred from the viewpoint of pressure sensitivity.

When the silver halide grains have such a structure as described above,a boundary between the parts having different halogen compositions fromeach other may be clear or an indistinct boundary wherein a mixedcrystal is formed by the difference in halogen compositions. Further,the boundary may be such a structure that the composition iscontinuously changed.

In the high silver chloride emulsions, a structure is preferred in whichsilver bromide rich phases are localized in a laminar or non-laminarform in the interiors of silver halide grains and/or on the surfacesthereof. With regard to the halogen composition of the localized phases,the silver bromide content thereof is preferably at least 10 mol %, morepreferably higher than 20 mol %. The localized phases may exist in theinteriors of the grains and on the edges, corners or planes of thesurfaces of the grains. However, it is particularly preferred that thelocalized phases exist on the corners of the grains.

There can be preferably used uniform structure type grains wherein thehalogen composition distribution in the grains is small to inhibit alowering in sensitivity when pressure is applied to the light-sensitivematerial.

Silver halide grains contained in the silver halide emulsions of thepresent invention have a mean grain size (the diameter of the grain isdefined as the diameter of a circle having an area equal to theprojected area of the grain, and the average of the diameters of thegrains is referred to as mean grain size) of preferably 0.1 to 2 μm.

The coefficient of variation (obtained by dividing the standarddeviation of a grain size distribution by the mean grain size) in thegrain size distribution is not higher than 20%, preferably not higherthan 15%, more preferably not higher than 10%, most preferably nothigher than 7%. Namely, a monodisperse system is preferred. It is oftenpreferred that a blend of monodisperse emulsions is added to the samelayer or the monodisperse emulsions are coated in the form of amulti-layer to obtain a wide latitude.

The silver halide grains of the present invention may have a regularcrystal form such as cube, tetradecahedron or octahedron, an irregularcrystal form such as sphere or platy form or a complex form of thesecrystal forms. A mixture of grains having various crystal forms may beused. In the present invention, it is preferred that grains have such agrain size distribution in which at least 50%, preferably at least 70%,more preferably at least 90%, of grains are composed of grains havingthe aforesaid crystal forms.

Further, there can be preferably used emulsions wherein tabular grainshaving an average aspect ratio (diameter in terms of a circle/thickness)of .not lower than 5, preferably not lower than 8, account for more than50% of the projected area of the entire grains.

Emulsions which can be used in the present invention can be prepared byusing the methods described in P. Glafkides, Chimie et PhisiquePhotographiue (Paul Montel 1967); G. F. Duffin, Photographic EmulsionChemistry (Focal Press 1966); and V. L. Zelikman et al., Making andCoating Photographic Emulsion (Focal Press 1966). Namely, an acidprocess, a neutral process or an ammonia process can be used. A solublesilver salt can be reacted with a halide by the single jet process, thedouble jet process or a combination thereof. A reverse mixing methodwherein grains are formed in the presence of an excess of silver ion canbe used. One type of the double jet process that can be used is acontrolled jet process wherein the pAg in the liquid phase in whichsilver halide is formed is kept constant. According to this processthere can be obtained a silver halide emulsion in which the crystal formis regular and the grain size is nearly uniform.

Various polyvalent metal ion impurities can be introduced into thesilver halide emulsions of the present invention during the course offormation of the emulsion grains or physical ripening thereof toincrease sensitivity or to improve reciprocity law characteristics,temperature and humidity dependence during exposure, or latent imagepreservability. Examples of compounds which can be used therefor includesalts of cadmium, zinc, lead, copper and thallium and salts and complexsalts of Group VIII elements such as iron, ruthenium, rhodium, palladiumosmium, iridium and platinum. The Group VIII elements are particularlypreferred. The amounts of these compounds to be used widely varydepending on purpose, but are preferably 10⁻⁹ to 10⁻² mol per mol ofsilver halide.

The silver halide emulsions of the present invention are subjected tochemical sensitization and spectral sensitization.

Chemical sensitization includes sulfur sensitization (typically the useof amorphous sulfur compounds), selenium sensitization, noble metalsensitization such as gold sensitization, and reduction sensitization.These sensitization methods may be used either alone or in combination.

Spectral sensitization is carried out to impart spectral sensitivity ina desired wavelength region of light to the emulsion in each layer ofthe light-sensitive material of the present invention. It is preferredthat spectral sensitization is carried out by adding dyes which absorblight in a wavelength region corresponding to the desired spectralsensitivity, that is, by adding spectral sensitizing dyes. Examples ofthe spectral sensitizing dyes which can be used in the present inventioninclude those described in F. M. Harmer, Heterocyclic Compounds-CyanineDyes and Related Compounds (John Wiley & Sons, New York, London 1964).The specific compounds and spectral sensitization methods described inJP-A-62-215272 (right upper column of page 22 to page 38) can bepreferably used in the present invention.

Various compounds or precursors thereof can be added to the silverhalide emulsions of the present invention to prevent the light-sensitivematerials from being fogged during the course of the preparation,storage or photographic processing thereof or to stabilize photographicperformance. Preferred examples of the compounds are described in theaforesaid JP-A-62-215272 (pp. 39-72).

The emulsions of the present invention may be a surface latent imageemulsion wherein a latent image is predominantly formed on the surfaceof the grain and internal latent image type emulsions wherein a latentimage is predominantly formed in the interior of the grain.

Gelatin which is used in the present invention is preferably deionized.Usually, gelatin contains a large amount of calcium ion, often 5000 ppmor more. It is preferred that deionized gelatin containing not more than500 ppm of calcium ion is used in the present invention. The deionizedgelatin is used in an amount of preferably at least 10% by weight, morepreferably at least 20% by weight, particularly preferably at least 50%by weight, based on the total amount of all the gelatins. Such deionizedgelatin may be added to any layer.

It is preferred that dyes (particularly oxonol dyes) capable of beingdecolorized by the processing described in European Patent 0,337,490A2(pp. 27-76) are added to the hydrophilic colloid layers of thelight-sensitive materials of the present invention in such an amount asto give an optical reflection density of not lower than 0.70 at 680 nm,or at least 12% by weight (more preferably at least 14% by weight) oftitanium oxide surface-treated with a bivalent to tetravalent alcohol(e.g., trimethylol ethane) is incorporated into the water-resistantlayer of the support to improve the sharpness, etc., of the image.

It is preferred that photographic additives such as cyan, magenta andyellow couplers are dissolved in high-boiling organic solvents. Anycompound can be used as a high-boiling organic solvent, so long as thecompound has a melting point of not higher than 100° C. and a boilingpoint of not lower than 140° C. and are water-immiscible and goodsolvents for couplers. The boiling points of the high-boiling organicsolvents are preferably not lower than 160° C. and more preferably notlower than 170° C.

The details of these high-boiling organic solvents are described inJP-A-62-215272 (right lower column of page 137 to right upper column ofpage 144).

Further, cyan, magenta or yellow couplers may be impregnated withloadable latex polymers (e.g., those described in U.S. Pat No.4,203,716) in the presence or absence of the high-boiling organicsolvent, or are dissolved together with water-insoluble, organicsolvent-soluble polymers and can be emulsified and dispersed in anaqueous solution of hydrophilic colloid.

Preferably, homopolymers or copolymers described in U.S. Pat No.4,857,449 (7th to 15th columns) and PCT WO88/00723 can be used. The useof methacrylate or acrylamide polymers, particularly acrylamide polymersis more preferred from the viewpoint of the stabilization of dye images.

It is preferred that the dye image preservability improving compoundsdescribed in European Patent 0,277,589A2 together with couplers,particularly pyrazoloazole couplers, are used in the light-sensitivematerials of the present invention.

Namely, it is preferred from the viewpoint of preventing stain frombeing formed by the formation of developed color by the reaction ofcouplers with a color developing agent or the oxidation product thereofleft behind in the layers during storage after processing and preventingother side effects from being caused, that a compound (F) and/or acompound (G) singly or in combination are/is used. Compound (F) ischemically bonded to an aromatic amine developing agent left behindafter color development to form a compound which is chemically inert andsubstantially colorless, and said compound (G) is chemically bonded tothe oxidation product of an aromatic amine color developing agent leftbehind after color development to form a compound which is chemicallyinert and substantially colorless.

It is also preferred that the antifungal agents described inJP-A-63-271247 are added to the light-sensitive materials of the presentinvention to prevent various molds or bacteria from growing in thehydrophilic colloid layers and deteriorating the image.

Examples of supports which can be used for the light-sensitive materialsof the present invention include white polyester supports for displayand supports in which a layer containing a white pigment is provided onthe silver halide emulsion layer side of the support. Further, it ispreferred that an antihalation layer is coated on the silver halideemulsion layer side of the support or on the back side thereof. It ispreferred that the transmission density of the support is set in therange of 0.35 to 0.8 so that display can be enjoyed by both reflectedlight and transmitted light.

The light-sensitive materials of the present invention may be exposed tovisible light or infrared light. The exposure method may be alow-illumination exposure or a high-illumination exposure. In the lattercase, a laser scanning exposure system wherein the exposure time per onepixel is shorter than 10⁻⁴ sec. is preferred

It is preferred that when exposure is conducted, band stop filterdescribed in U.S. Pat. No. 4,880,726 is used, whereby light color mixingcan be removed and color reproducibility can be greatly improved.

It is preferred that after exposure, the color photographic materials ofthe present invention are subjected to color development,bleaching-fixing and rinsing treatment (or stabilizing treatment).Bleaching and fixing may be carried out with one bath as described aboveor may be separately carried out. The processing time of the colorphotographic materials of the present invention taken from colordevelopment to rinsing treatment (or stabilizing treatment) is within 4minutes, preferably within 3 minutes.

Silver halide emulsions, other materials (e.g., additives), photographicconstituent layers (e.g., layer arrangement), processing methods andprocessing additives described in the following patent specifications,particularly European Patent 0,355,660A2 (JP-A-2-139544) can bepreferably applied to the light-sensitive materials of the presentinvention.

Photographic constituent element, etc. JP-A-62-215272 JP-A-2-33144 EP0,355,660A2 Silver halide Line 6 of right upper column Line 16 of rightupper Line 53 of p. 45 to emulsion of p. 10 to line 5 of left column ofp. 28 to line line 3 of p. 47; and lower column of p. 12; and 11 ofright lower line 20 to line 22 line 4 from the bottom of column of p.29; and of p. 47 p. 12 to line 17 of left line 2 to line 5 of p. 30upper column of p. 13 Solvent for Line 6 to line 14 of left — — silverhalide lower column of p. 12; and line 3 from the bottom of left uppercolumn of p. 13 to the bottom of left lower column of p. 18 ChemicalLine 3 of left lower column Line 12 to the bottom Line 4 to Line 9 ofsensitizing to line 5 from the bottom of right lower column of p. 47agent of right lower column of p. 29 p. 12; and line 1 of right lowercolumn of p. 18 to line 9 from the bottom of right upper column of p. 22Spectral Line 8 from the bottom of Line 1 to line 13 of left Line 10 toline 15 of sensitizing right upper column of p. 22 upper column of p. 30p. 47 dye (spectral to the bottom of p. 38 sensitizing method) EmulsionLine 1 of left upper column Line 14 of left upper Line 16 to line 19 ofstabilizer of p. 39 to the bottom of column to line 1 of right p. 47right upper column of p. 72 upper column of p. 30 Development Line 1 ofleft lower column — — accelerator of p. 72 to line 3 of right uppercolumn of p. 91 Color coupler Line 4 of right upper column Line 14 ofright upper Line 15 to line 27 (cyan, magenta, of p. 91 to line 6 ofleft column of p. 3 to the bottom of p. 4; line 30 yellow coupler) uppercolumn of p. 121 of left upper column of p. 5 to the bottom of p. 18;and line 6 of of p. 28; line 29 to right upper column of p. 30 line 31of p. 45; and to line 11 of right lower line 23 of p. 47 to column of p.35 line 50 of p. 63 Super— Line 7 of left upper column — — sensitizingof p. 121 to line 1 of right agent upper column of p. 125 UltravioletLine 2 of right upper column Line 14 of right lower Line 22 to line 31of light of p. 125 to the bottom of column of p. 37 to line 11 p. 65absorber left lower column of p. 127 of left upper column of p. 38Anti-fading Line 1 of right lower column Line 12 of right upper Line 30of p. 4 to agent (image of p. 127 to line 8 of left column of p. 36 toline 19 line 23 of p. 5; line stabilizer) lower column of p. 137 of leftupper column of 1 of p. 29 to line 25 p. 37 of p. 45; line 33 to line 40of p. 45; and line 2 to line 21 of p. 65 High-boiling Line 9 of leftlower column Line 14 of right lower Line 1 to line 51 of and/or low- ofp. 137 to the bottom of column of p. 35 to line 4 p. 64 boiling rightupper column of from the bottom of left organic p. 144 upper column ofp. 36 solvent Dispersion Line 1 of left lower column Line 10 of rightlower Line 51 of p. 63 to method of p. 144 to line 7 of column of p. 27to the line 56 of p. 64 of photo- right upper column bottom of leftupper column graphic of p. 146 of p. 28; and line 12 of additive rightcolumn of p. 35 to line 7 of right upper column of p. 36 Hardening Line8 of right upper column — — agent of p. 146 to line 4 of left lowercolumn of p. 155 Developing Line 5 of left lower column agent of p. 15to line 2 of right precursor lower column of p. 155 Development Line 3to line 9 of right — — restrainer lower column of p. 155 releasingcompounds Support Line 19 of right lower Line 18 of right upper Line 29of p. 66 to column of p. 155 to line 14 column of p. 38 to line 3 line13 of p. 67 of left upper column of of left upper column of p. 156 p. 39Constitution Line 15 of left upper Line 1 to line 15 of Line 41 to line52 of light— column of p. 156 to line 14 right upper column 8 of p. 45sensitive of right lower column of p. 28 layer of p. 156 Dye Line 15 ofright lower Line 12 of left lower Line 18 to line 22 of column of p. 156to the column to line 7 of right p. 66 bottom of right lower uppercolumn of p. 38 column of p. 154 column Color mixing Line 1 of leftupper column Line 8 to line 11 of Line 57 of p. 64 to inhibitor of p.185 to line 3 of right upper column of line 1 of p. 65 right lowercolumn of p. 36 p. 188 Gradation Line 4 to line 8 of right — controllerlower column of p. 188 Anti- Line 9 of right lower column The bottom ofleft upper Line 32 of p. 65 to staining of p. 188 to line 10 of columnto line 13 of right line 17 of p. 66 agent right lower column of p. 193lower column of p. 37 Surfactant Line 1 of left lower column Line 1 ofright upper column — of p. 201 to the bottom of of p. 18 to the bottomof right upper column of p. 210 right lower column of p. 24; and line 10from the bottom of left lower column to line 9 of right lower columnFluorine- Line 1 of left lower column Line 1 of left upper column —containing of p. 210 to line 5 of of p. 25 to line 9, compound (as leftlower column of p. 222 right lower column of p. 27 antistatic agent,coating aid, lubricant, sticking inhibitor, etc.) Binder Line 6 of leftlower column Line 8 to line 18 of Line 23 to line 28 (hydrophilic of p.222 to the bottom of right upper column of p. 38 of p. 66 colloid) leftupper column of p. 225 Thickener Line 1 of right upper column — — of p.225 to line 2 of right upper column of p. 227 Antistatic Line 3 of rightupper column — — agent of p. 227 to line 2 of left upper column of p.23) Polymer latex Line 2 of left upper column — — of p. 230 to thebottom of p. 239 Matting agent Line 1 of left upper column — — of p. 240to the bottom of right upper column of p. 240 Photographic Line 7 ofright upper column Line 4 of left upper column Line 14 of p. 67 toprocessing of p. 3 to line 5 of right of p. 39 to the bottom of line 28of p. 69 (processing upper column of p. 10 left upper column of p. 42stage, additives. etc.) Note: The above cited passages of JP-A-62-215272include the amended matters in the amendment dated March 16, 1987, whichis attached to the end of the publication.

As cyan couplers, the above-described cyan couplers may be used togetherwith the diphenylimidazole cyan couplers described in JP-A-2-33144, the3-hydroxypyridine cyan couplers (particularly two equivalent typecouplers formed by introducing a chlorine-eliminatable group into fourequivalent type couplers such as coupler (42), and further couplers (6)and (9) are preferred) described in European Patent 0,333,185A2 or thecyclic active methylene cyan couplers (particularly couplers 3, 8 and 34are preferred) described in JP-A-64-32260.

The processing methods described in JP-A-2-207250 (left upper column ofpage 27 to right upper column of page 34) can be preferably applied tothe processing of the silver halide color photographic materials usinghigh silver chloride emulsions having a silver chloride content of notlower than 90 mol %.

The present invention is now illustrated in greater detail by referenceto the following examples which, however, are not to be construed aslimiting the present invention in any way.

EXAMPLE 1

The following layers were coated on a paper support (both sides thereofwere laminated with polyethylene) to prepare multi-layer colorphotographic paper. Coating solutions were prepared in the followingmanner.

Fifteen g of a yellow coupler (compound Y-31), 0.4 g of a compound ofgeneral formula (II) (compound II-10), 4.0 g of a dye image stabilizer(Cpd-1) and 2.0 g of a sodium dodecylbenzenesulfonate were added to 5.0g of a solvent (Solv-1) and 25 cc of ethyl acetate to dissolve them. Theresulting solution was emulsified and dispersed in a 10% aqueoussolution of gelatin in a homogenizer.

Separately, the following blue-sensitive Sensitizing Dyes A and B wereadded to a silver chlorobromide Emulsion A (cubic, a 3:7 (by Ag molarratio) mixture of a larger-size emulsion B₁ having a mean grain size of0.88 μm and a smaller-size emulsion B₂; a coefficient of variation ingrain size: 0.06 and 0.08, respectively; 0.3 mol % of silver bromidebeing localized on a part of the surface of the grain in each emulsion)(2.0×10⁻⁴mol of each of the Sensitizing Dyes A and B was added to thelarger-size emulsion, and 2.5×10⁻⁴ mol of each of the sensitizing dyeswas added to the smaller-size emulsion, each amount being per mol ofsilver halide). The chemical ripening of the emulsion was carried out byadding a sulfur sensitizing agent and a gold sensitizing agent. Theemulsion and the above emulsified dispersion were mixed and dissolved,and a coating solution for the first layer was prepared so as to givethe following composition described as First Layer.

Coating solutions for the second layer through the seventh layer wereprepared in the same manner as in the preparation of the coatingsolution for the first layer.

Sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as a hardeningagent for the gelatin in each layer. Further, Cpd-10 and Cpd-11 wereadded to each layer in such an amount as to give 25.0 mg/m² and 50.0mg/m² in terms of the total amount.

The following spectral sensitizing dyes were used for the silverchlorobromide emulsion of each light-sensitive emulsion layer:

Blue-Sensitive Emulsion Layer

Sensitizing Dye A

(2.0×10⁻⁴ of each dye being added to the larger-size emulsion, and2.5×10⁻⁴ mol of each dye being added to the smaller-size emulsion, eachamount being per mol of silver halide);

Green-Sensitive Emulsion Layer

(4.0×10⁻⁴ mol being added to the larger-size emulsion, and 5.6×10⁻⁴ molbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide);

(7.0×10⁻⁵ mol being added to the larger-size emulsion, and 1.0×10⁻⁵ molbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide);

Red-Sensitive Emulsion Layer

(0.9×10⁻⁴ mol being added to the larger-size emulsion, and 1.1×10⁻⁴ molbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide).

Further, 2.6×10⁻³ mol of the following compound per mol of silver halidewas added to the red-sensitive emulsion layer:

Further, 3.4×10⁻⁴ mol, 9.7×10⁻⁴ mol, and 5.5×10⁻⁴ mol of1-(5-methylureidophenyl)-5-mercaptotetrazole per mol of silver halidewere added to the blue-sensitive emulsion layer, the green-sensitiveemulsion layer and the red-sensitive emulsion layer, respectively.Furthermore, 1×10⁻⁴ mol, 2×10⁻⁴ mol of4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mol of silver halide wereadded to the blue-sensitive emulsion layer and the green-sensitiveemulsion layer, respectively.

The following dyes (parenthesized numbers indicating coating weights)were added to the emulsion layers:

Layer Structure

Each layer had the following composition, The numbers represent coatingweight (g/m²), The amounts of the silver halide emulsions are coatingweight in terms of silver.

Support

Polyethylene-laminated paper

[Polyethylene on the first layer side contained white pigment (TiO₂) andbluish dye (ultramarine)]

First Layer (yellow color forming emulsion layer) The above silverchlorobromide emulsion 0.27 Gelatin 1.36 Yellow coupler (Compound Y-31)0.75 Compound of formula (II) 0.02 (compound II-10) 0.20 Dye imagestabilizer (Cpd-1) 0.25 Solvent (Solv-1) Second layer (color mixinginhibiting layer) (10 mg/m²) (10 mg/m²) (40 mg/m²) (20 mg/m²) Gelatin0.99 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-7) 0.02 Solvent(Solv-2) 0.25 Solvent (Solv-3) 0.25 Third Layer (magenta color formingemulsion layer) Silver chlorobromide emulsion (cubic, 0.13 a 6:4 (by Agmolar ratio) mixture of a larger-size emulsion G₁ having a mean grainsize of 0.55 μm and a smaller-size emulsion G₁ having a mean grain sizeof 0.39 μm; a coefficient of variation in grain size distribution: 0.10and 0.08; 0.8 mol of AgBr being localized on a part of the surface ofthe grain in each emulsion) Gelatin 1.45 Magenta coupler (ExM) 0.16 Dyeimage stabilizer (Cpd-6) 0.15 Dye image stabilizer (Cpd-2) 0.03 Dyeimage stabilizer (Cpd-7) 0.01 Dye image stabilizer (Cpd-8) 0.01 Dyeimage stabilizer (Cpd-9) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4)0.15 Solvent (Solv-5) 0.15 Fourth Layer (color mixing inhibiting layer)Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-7) 0.01Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Fifth Layer (cyan colorforming emulsion layer) Silver chlorobromide emulsion (cubic, 0.20 a 7:3(by Ag molar ratio) mixture of a larger-size emulsion R₁ having a meangrain size of 0.58 μm and a smaller-size emulsion R₂ having a mean grainsize of 0.45 μm; a coefficient of variation in grain-size distri-bution: 0.09 and 0.11; 0.6 mol % of AgBr being localized on a part ofthe surface of the grain in each emulsion) Gelatin 0.85 Cyan coupler(ExC) 0.33 Ultraviolet light absorber (UV-2) 0.18 Dye image stabilizer(Cpd-1) 0.33 Dye image stabilizer (Cpd-10) 0.15 Dye image stabilizer(Cpd-11) 0.15 Dye image stabilizer (Cpd-12) 0.01 Dye image stabilizer(Cpd-9) 0.01 Dye image stabilizer (Cpd-7) 0.01 Solvent (Solv-6) 0.22Solvent (Solv-1) 0.01 Sixth Layer (ultraviolet light absorbing layer)Gelatin 0.55 Ultraviolet light absorber (UV-1) 0.42 Dye image stabilizer(Cpd-13) 0.15 Dye image stabilizer (Cpd-6) 0.02 Seventh layer(protective layer) Gelatin 1.13 Acrylic-modified copolymer of 0.15polyvinyl alcohol (a degree of modification: 17%) Liquid paraffin 0.03Dye image stabilizer (Cpd-14) 0.01

The compounds used above are the following:

The thus-obtained sample was referred to as Sample 101.

Samples 102 to 117 were prepared in the same manner as in thepreparation of Sample 101, except that the compositions of compounds ineach layer were changed as indicated in Table 4.

Sample 101 was subjected to gray exposure so as to allow about 30% ofthe amount of silver coated to be developed by using a sensitometer (FWHtype, color temperature of light source: 3200° K, manufactured by FujiPhoto Film Co., Ltd.).

After completion of exposure, the exposed sample was subjected tocontinuous processing by using a paper processor and the followingprocessing solutions having the following compositions in the followingprocessing stages to prepare the processed state of running equilibriumstate.

Tank Processing Stage Temp. Time Replenisher* capacity Color 35° C. 45sec 161 ml 171 development Bleach-fixing 30-35° C. 45 sec 215 ml 171Rinse 30° C. 90 sec 350 ml 101 Drying 70-80° C. 60 sec *Replenishmentrate being per m² of light-sensitive material

Each processing solution had the following composition.

Tank Solution Replenisher Color developer solution Water 800 ml 800 mlEthylenediamine-N,N,N′,N′- 1.5 g 2.0 g tetramethylenephosphonic acidPotassium bromide 0.015 g — Triethanolamine 8.0 g 12.0 g Sodium chloride1.4 g — Potassium carbonate 25 g 25 g N-Ethyl-N-(β-methanesulfon- 5.0 g7.0 g amidoethyl)-3-methyl-4-amino- aniline sulfateN,N-Di(carboxymethyl)- 4.0 g 5.0 g hydrazine N,N-Di(sulfoethyl)- 4.0 g5.0 g hydroxylamime mono Na salt Fluorescent brightener 1.0 g 2.0 g(WHITEX 4B manufactured by Sumitomo Chemical Co., Ltd.) Add water tomake 1000 ml 1000 ml pH (25° C.) 10.05 10.45 Bleach-fixing solution(Tank solution and replenisher being the same) Water 400 ml Ammoniumthiosulfate (700 g/l) 100 ml Sodium sulfite 17 g Ammoniumethylenediaminetetraacetato 55 g ferrate (III) Disodiumethylenediaminetetracetate 5 g Ammonium bromide 40 g Add water to make1000 ml pH (25° C.) 6.0

Rinsing Solution

(Tank solution and replenisher being the same)

Ion exchanged water (the concentration of each of calcium ion andmagnesium ion being reduced to not higher than 3 ppm).

Each of Samples 101 to 117 was subjected to gradation exposure through athree color separation filter for sensitometry by using a sensitometer(FWH type manufactured by Fuji Photo Film Co., Ltd.) and then subjectedto color development in the above-described processing stages.

The samples processed in the manner described above were evaluated inthe following manner:

(a) White ground after processing

The processed samples were randomly arranged, and yellowing on the whiteground was organoleptically evaluated in the following three grades:

O: unnoticed

Δ: noticeable, but acceptable

X: not acceptable

(b) Fastness to light

An under glass outdoor exposure stand was used, and a fading test wascarried out under sunlight for two months. The relative residual density[D/D₀(%)] to an initial density after fading at an initial density of1.0 was calculated. A rise in stain on the white ground was determinedby measuring the increase in (ΔDy-min) yellow density.

(c) Yellow color developability

Maximum density (Dmax) in developed yellow color areas was measured byusing X-rite densitometer.

The results of the evaluation of Samples 101 to 117 are shown in Table4.

TABLE 4 Amount Color Compound of of ultraviolet White develop- Sampleformula (II) light absorber used ground after Fastness to light abilityNo type amount 5th layer 6th layer processing D/D₀ (%) ΔDy-min DmaxRemarks 101 II-10 0.02 0.18 0.42 ◯ 87 0.01 2.47 Invention 102 II-10 0.040.18 0.42 ◯ 90 0.01 1.44 Invention 103 II-10 0.06 0.18 0.42 ◯ 93 0.012.38 Invention 104 — — — — ◯ 50 0.08 2.50 Comp. Ex. 105 II-10 0.02 — — ◯60 0.07 2.47 Comp. Ex. 106 II-10 0.04 — — ◯ 67 0.06 2.44 Comp. Ex. 107II-10 0.06 — — ◯ 70 0.05 2.38 Comp. Ex. 108 — — 0.18 0.21 ◯ 58 0.07 2.50Comp. Ex. 109 — — 0.18 0.42 ◯ 62 0.06 2.50 Comp. Ex. 110 — — 0.18 0.84 Δ65 0.05 2.50 Comp. Ex. 111 — — 0.18 1.26 X 67 0.05 2.50 Comp. Ex. 112Comparative 0.02 — — ◯ 53 0.07 2.40 Comp. Ex. compound* 113 Comparative0.04 — — ◯ 56 0.06 2.20 Comp. Ex. compound* 114 Comparative 0.06 — — ◯58 0.05 2.02 Comp. Ex. compound* 115 Comparative 0.02 0.18 0.42 ◯ 630.06 2.40 Comp. Ex. compound* 116 Comparative 0.04 0.18 0.42 ◯ 65 0.052.20 Comp. Ex. compound* 117 Comparative 0.06 0.18 0.42 ◯ 67 0.05 2.02Comp. Ex. compound* *Comparative compound

(described in JP-B-48-31625) Note: Amount of compound in Table is g/m²

It will be understood from Table 4 that fastness to light is improved byusing either a compound of formula (II) alone or an ultraviolet lightabsorber alone (Sample Nos. 104 to 114), in comparison with the casewhere neither the compound of formula (II) nor the ultraviolet lightabsorber is added or the cases in which comparative bisphenol compoundsare used. When comparative bisphenol compounds are used, colordevelopability is greatly lowered. Even when the amount of theultraviolet light absorber is increased in the case of the use of theultraviolet light absorber alone, an effect of improving fastness tolight is saturated and the degree of yellowing on the white ground isnot acceptable.

On the other hand, when a compound of formula (II) and an ultravioletlight absorber are used in combination (Sample Nos. 101 to 103),fastness to light can be greatly improved in comparison with the casewhere a compound of formula (II) alone or an ultraviolet light absorberalone is used. Accordingly, it can be seen that an effect of remarkablyimproved fastness to light can be obtained by using a compound offormula (II) and an ultraviolet light absorber in combination.

A similar effect could be obtained when the Compound II-13 or II-23 wasused in place of the Compound II-10 in the samples of the presentinvention.

EXAMPLE 2

Sample Nos. 201 to 214 were prepared in the same manner as in thepreparation of Sample No. 101 of Example 1, except that a 1:1 (byweight) mixture of yellow couplers Y-31 and Y-2 was used in place of theyellow coupler used in Sample No. 101, ultraviolet light absorber UV-3was used in place of the ultraviolet light absorber used in the sixthlayer of Sample No. 101, and further compounds indicated in Table 5 wereused in the amounts shown. In the same manner as in Example 1,processing and evaluation were made. The results are shown in Table 5.

TABLE 5 Amount Epoxy Color Compound of of ultraviolet compound Fastnessdevelop- Sample formula (II) light absorber used of invention to lightability No. type amount 5th layer 6th layer type amount D/D₀ (%) DmaxRemarks 201 II-10 0.06 — — — — 65 2.42 Comp. Ex. 202 II-4 0.06 — — — —63 2.40 Comp. Ex. 203 — — 0.22 0.38 — — 60 2.54 Comp. Ex. 204 — — — — —— 48 2.54 Comp. Ex. 205 II-10 0.06 0.22 0.38 — — 90 2.42 Invention 206II-4 0.06 0.22 0.38 — — 90 2.40 Invention 207 II-10 0.06 0.22 0.38 A-35*0.10 92 2.55 Invention 204 II-4 0.06 0.22 0.38 A-35* 0.20 92 2.55Invention 209 II-10 0.06 0.22 0.38 A-34* 0.10 92 2.55 Invention 210 II-40.06 0.22 0.38 A-34* 0.20 91 2.54 Invention 211 II-23 0.06 0.22 0.38A-10 0.10 90 2.54 Invention 212 II-10 0.06 0.22 0.38 A-18 0.10 92 2.55Invention 213 II-10 0.06 0.22 0.38 A-36* 0.10 91 2.55 Invention 214II-10 0.06 0.22 0.38 A-48 0.10 91 2.55 Invention Note: The amount of thecompound in Table is g/m². *In A-34, A-35 and A-36, x is 7.5

It can be seen from Table 5 that fastness to light can be greatlyimproved when a compound of formula (II) and an ultraviolet lightabsorber are used in combination (Sample Nos. 205 and 206). Further,when the epoxy compound of the present invention is used togethertherewith, the problem with regard to a lowering in the developabilityof yellow coupler caused by the compound of formula (II) can be solved,and a high color density can be obtained (Sample Nos. 207 to 214).

EXAMPLE 3

Samples were prepared in the same manner as in the preparation of SampleNo. 207 of Example 2, except that an equal weight of yellow coupler Y-2,Y-6, Y-12, Y-20 or Y-34 was used in respective samples in place of Y-31.In the same manner as in Example 2, evaluation was made. It was foundthat when a compound of formula (II) and an ultraviolet light absorberwere used in combination, fastness to light could be greatly improved.Further, when the epoxy compound was used, color developability wasgood.

EXAMPLE 4

The following layers having the following compositions were coated on apaper support (both sides of the support were laminated withpolyethylene to prepare a multi-layer color photographic paper. Coatingsolutions were prepared in the following manner.

Fifteen g of yellow coupler (compound Y-31), 2.0 g of dye imagestabilizer (A-35), 5.0 g of compounds of general formula (IV) (compoundIV-I), 0.4 g of dye image stabilizer (Cpd-2), 2.0 g of dye imagestabilizer (Cpd-1) and 2.0 g of sodium dodecylbenzenesulfonate weredissolved in 25 cc of ethyl acetate. The resulting solution wasemulsified and dispersed in 150 cc of an aqueous solution of 10%lime-processed ossein gelatin (containing 1.5 g of citric acid) using ahomogenizer.

Separately, the following blue-sensitive Sensitizing Dyes A and B wereadded to a silver chlorobromide emulsion (cubic, a 5:5 (by silver molarratio) mixture of a larger-size Emulsion B₁ having a mean grain size of0.85 μm and a smaller-size Emulsion B₂ having a mean grain size of 0.65μm; a coefficient of variation in grain size distribution: 0.07 and0.09, respectively; 0.2 mol % of silver bromide being localized on apart of the surface of the grain in each emulsion) in such an amountthat 2.2×10⁻⁴ mol of each of Sensitizing Dyes A and B was added to thelarger emulsion, and 2.7×10⁻⁴ mol of each of the sensitizing dyes wasadded to the smaller-size emulsion. The chemical ripening of theemulsion was carried out by adding a sulfur sensitizing agent and a goldsensitizing agent. The emulsion and the above emulsified dispersion weremixed and dissolved, and a coating solution for first layer was preparedso as to give the following composition named as First Layer.

Coating solutions for the second layer through the seventh layer wereprepared in the same manner as in the preparation of the coatingsolution for the first layer.

Sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as a hardeningagent for gelatin in each layer. Cpd-10 and Cpd-11 were added to eachlayer in such an amount that the total amounts became 25.0 mg/m² and50.0 mg/m², respectively.

The following spectral sensitizing dyes were used in the silverchlorobromide emulsion of each light-sensitive emulsion layer.

Blue Sensitive Emulsion Layer

(2.0×10⁻⁴ mol of each of sensitizing dyes A and B being added to thelarger-size emulsion, and 2.5×10⁻⁴ mol of each of the sensitizing dyesbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide);

Green-Sensitive Emulsion Layer

(4.0×10⁻⁴ mol being added to the larger-size emulsion, and 5.6×10⁻⁴ molbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide);

(7.0×10⁻⁵ mol being added to the larger-size emulsion, and 1.0×10⁻⁵ molbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide);

Red-Sensitive Emulsion Layer

(0.9×10⁻⁴ mol being added to the larger-size emulsion, and 1.1×10⁻⁴ molbeing added to the smaller-size emulsion, each amount being per mol ofsilver halide).

Further, 2.6×10⁻³ mol of the following compound per mol of silver halidewas added to the red-sensitive emulsion layer:

Further, 3.4×10⁻⁴ mol, 9.7×10⁻⁴ mol and 5.5×10⁻⁴ mol of1-(5-methylureidophenyl)-5-mercaptotetrazole were added to theblue-sensitive emulsion layer, the green-sensitive emulsion layer andthe red-sensitive emulsion layer, respectively, each amount being permol of silver halide. Furthermore, 1×10⁻⁴ mol and 2×10⁻⁴ mol of4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to theblue-sensitive layer and the green-sensitive layer, respectively, eachamount being per mol of silver halide.

The following dyes (parenthesized numbers indicating coating weight)were added to the emulsions to prevent irradiation:

Layer Structure

Each layer had the following composition. The numbers represent coatingweight (g/m²). The amounts of the silver halide emulsions arerepresented by coating weight in terms of silver.

Support

Polyethylene-laminated paper

[Polyethylene on the first layer side contained white pigment (TiO₂) andbluish dye (ultramarine)]

First layer (yellow color forming emulsion layer) The above silverchlorobromide emulsion 0.27 Gelatin 1.10 Yellow coupler (Compound Y-31)0.75 Epoxy compound of invention (Compound A-35) 0.02 Dye imagestabilizer (Cpd-2) 0.02 Dye image stabilizer (Cpd-1) 0.20 Solvent(Solv-1) 0.25 Second layer (color mixing inhibiting layer) (10 mg/m²)(10 mg/m²) (40 mg/m²) (20 mg/m²) Gelatin 0.99 Color mixing inhibitor(Cpd-4) 0.08 Solvent (Solv-7) 0.02 Solvent (Solv-2) 0.25 Solvent(Solv-3) 0.25 Third layer (magenta color forming emulsion layer) silverchlorobromide emulsion 0.13 (cubic, a 6:4 (by Ag molar ratio) mixture ofa larger-size emulsion G₁ having a mean grain size of 0.52 and asmaller-size emulsion G₂ having a mean grain size of 0.42 μm; acoefficient of variation in grain size distribution: 0.10 and 0.08,respectively; 0.8 mol % of AgBr being localized on a part of the surfaceof the grain in each emulsion) Gelatin 1.45 Magenta coupler (ExM) 0.16Dye image stabilizer (Cpd-6) 0.15 Dye image stabilizer (Cpd-2) 0.03 Dyeimage stabilizer (Cpd-7) 0.01 Dye image stabilizer (Cpd-8) 0.01 Dyeimage stabilizer (Cpd-9) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4)0.15 Solvent (Solv-5) 0.15 Fourth layer (color mixing inhibiting layer)Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0.02Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.20 Fifth layer (cyan colorforming emulsion layer) silver chlorobromide emulsion 0.20 (cubic, a 7:3(by Ag molar ratio) mixture of a larger-size emulsion R₁ having a meangrain size of 0.58 μm and a smaller-size emulsion R2 having a mean grainsize of 0.45 μm; a coef- ficient of variation in grain sizedistribution: 0.09 and 0.11, respectively; 0.6 mol % of AgBr beinglocalized on a part of the surface of the grain in each emulsion)Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet light absorber (UV-2)0.18 Dye image stabilizer (Cpd-1) 0.33 Dye image stabilizer (Cpd-10)0.15 Dye image stabilizer (Cpd-11) 0.15 Dye image stabilizer (Cpd-12)0.01 Dye image stabilizer (Cpd-9) 0.01 Dye image stabilizer (Cpd-7) 0.01Solvent (Solv-6) 0.22 Solvent (Solv-1) 0.01 Sixth layer (ultravioletlight absorbing layer) Gelatin 0.55 Ultraviolet light absorber (UV-1)0.42 Dye image stabilizer (Cpd-13) 0.15 Dye image stabilizer (Cpd-6)0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic-modifiedcopolymer of poly- 0.15 vinyl alcohol (degree of modification: 17%)Liquid paraffin 0.03 Dye image stabilizer (Cpd-14) 0.01

The compounds used above are the same as those disclosed in Example 1.

The thus-obtained sample was referred to as Sample No. 401.

Sample Nos. 402 to 409 were prepared in the same manner as in thepreparation of Sample No. 401, except that the composition of the firstlayer was changed as indicated in Table 6.

Sample No. 401 was subjected to gray exposure so as to allow about 30%of the amount of silver coated to be developed by using a sensitometer(FWH type, color temperature of light source: 3200° K, manufactured byFuji Photo Film Co., Ltd.).

After exposure, each exposed sample was subjected to continuousprocessing by using a paper processor and the following processingsolutions having the following compositions in the following processingstages to prepare the process state of running equilibrium state.

Processing Tank stage Temp. Time Replenisher* capacity Color 35° C. 45sec 161 ml 171 development Bleaching- 30˜35° C. 45 sec 215 ml 171 fixingRinse 30° C. 90 sec 350 ml 101 Drying 70˜80° C. 60 sec *Replenishmentrate being per m¹ of light-sensitive material

Each processing solution had the following composition.

Tank Solution Replenisher Color developer solution Water 800 ml 800 mlEthylenediamine-N,N,N′,N′- 1.5 g 2.0 g tetramethylenephosphoric acidPotassium bromide 0.015 g — Triethanolamine 8.0 g 12.0 g Sodium chloride1.4 g — Potassium carbonate 25 g 25 g N-Ethyl-N-(β-methane- 5.0 g 7.0 gsulfonamidoethyl)-3-methyl-4- aminoaniline sulfateN,N-Bis(carboxymethyl)- 4.0 g 5.0 g hydrazineN,N-Di(sulfoethyl)hydroxyl- 4.0 g 5.0 g amine mono-Na salt Fluorescentbrightener 1.0 g 2.0 g (WHITEX 4B manufactured Sumitomo Chemical Co.,Ltd.) Add water to make 1000 ml 1000 ml pH (25° C.) 10.05 10.45Bleach-fixing solution (Tank solution and replenisher being the same)Water 400 ml Ammonium thiosulfate (700 g/l) 100 ml Sodium sulfite 17 gAmmonium ethylenediaminetetraacetato 55 g ferrate (III) Disodiumethylenediaminetetracetate 5 g Ammonium bromide 40 g Add water to make1000 ml pH (25° C.) 6.0

Rinsing Water

(Tank solution and replenisher being the same)

Ion-exchanged water (the concentration of each of calcium ion andmagnesium ion being reduced to not higher than 3 ppm).

Each sample was evaluated in the following manner:

(A) Fluctuation in Gradation of Developed Yellow Color Area

Each of Sample Nos. 401 to 409 was subjected to gradation exposurethrough a three color separation filter for sensitometry by using asensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.), andprocessing with the processing solutions before continuous processing inthe above processing stages and processing in the running equilibriumstate were carried out.

In both processings, a change in gradient (gamma) of in the area rangingfrom a density of 0.8 to a density of 1.8 on the characteristics curveof developed yellow color area, i.e., Δgamma was determined. Fluctuationin gradation caused by processing is smaller the closer Δgamma to zero.Thus, a smaller Δgamma value is preferable.

(B) Preservability of Yellow Dye Image

The samples processed in the running equilibrium state in the above (A)were stored at 80° C. and 60% RH for 40 days. The ratio [D/D₀(%)] of adensity D after storage to an initial yellow density D₀ of 2.0 wascalculated. The fastness of the yellow dye image to light is higher thecloser the value to 100. Namely, a higher value is preferable.

Further, an increase (ΔD_(magenta)) in magenta density before and afterstorage at an initial yellow density of 2.0 and an increase (ΔD_(cyan))in cyan density before and after storage at an initial yellow density of2.0 were measured. A smaller ΔD_(magenta) and ΔD_(cyan) value means thatan increase in the turbidity of yellow color is smaller. Namely, asmaller value is preferable.

The above-described evaluation of Sample Nos. 401 to 409 was made. Theresults are shown in Table 6.

TABLE 6 Epoxy compound having Sample at least one group Compound of No.of formula (AO) formula (IV) Δgamma D/D₀ [%] ΔD_(magenta) ΔD_(cyan)Remarks 401 A-35 (x = 7.5) Solv-1 0.11 90 0.19 0.03 Invention 402 A-34(x = 7.5) Solv-1 0.11 90 0.19 0.03 Invention 403 A-35 (x = 7.5) — 0.4075 0.33 0.06 Comp. Ex. 404 A-34 (x = 7.5) — 0.40 72 0.33 0.06 Comp. Ex.405 A-35 (x = 7.5) Comparative 0.33 72 0.33 0.07 Comp. Ex. Compound A*406 A-34 (x = 7.5) Comparative 0.33 70 0.33 0.07 Comp. Ex. Compound A*407 — Solv-1 0.33 70 0.35 0.09 Comp. Ex. 408 — — 0.56 65 0.46 0.10 Comp.Ex. 409 — Comparative 0.42 65 0.46 0.10 Comp. Ex. Compound A**Comparative Compound A

It can be seen from Table 6 that only Sample Nos. 401 and 402 containingan epoxy compound having at least one group of formula (AO) and acompound of formula (IV) in combination cause scarcely any fluctuationin gradation (Δgamma) before and after running and are excellent in thepreservability of image in the developed yellow color area.

EXAMPLE 5

Sample Nos. 501 to 511 were prepared in the same manner as in thepreparation of Sample No. 401 of Example 4, except that an equimolaramount of a 1:1 (by weight) mixture of yellow couplers Y-31 and Y-2 wasused in place of Y-31 and further the compounds and the amounts thereofwere changed as indicated in Table 7In the same manner as in Example 4,processing and evaluation were made. The results are shown in Table 7.

TABLE 7 Epoxy compound having Sample at least one group Compound of No.of formula (AO) formula (IV) Δgamma D/D₀ [%] ΔD_(magenta) ΔD_(cyan)Remarks 501 A-35 (x = 7.5) Solv-1 0.10 91 0.18 0.03 Invention 502 A-35(x = 7.5) IV-5 0.11 90 0.18 0.03 Invention 503 A-35 (x = 7.5) IV-9 0.1090 0.19 0.03 Invention 504 A-35 (x = 7.5) IV-12 0.11 90 0.19 0.03Invention 505 A-10 Solv-l 0.11 91 0.19 0.04 Invention 506 A-18 Solv-l0.11 90 0.19 0.04 Invention 507 A-34 (x = 7.5) Solv-1 0.10 90 0.19 0.03Invention 508 A-36 (x = 5.5) IV-1 0.10 91 0.19 0.04 Invention 509 A-35(x = 7.5) — 0.41 72 0.34 0.08 Comp. Ex. 510 — Solv-1 0.35 69 0.37 0.09Comp. Ex. 511 — — 0.55 60 0.48 0.11 Comp. Ex.

It can be seen from Table 7 that only samples 501 to 508 containing anepoxy compound having at least one group of formula (AO) and a compoundof formula (IV) cause scarcely any fluctuation in gradation (Δgamma)before and after running and are excellent in the preservability ofimage in developed yellow color area.

EXAMPLE 6

Samples were prepared in the same manner as in the preparation of SampleNo. 401 of Example 4, except that an equimolar amount of yellow couplerY-2, Y-6, Y-12, Y-20 or Y-34 was used in respective samples in place ofY-31. In the same manner as in Example 4, evaluation was made. It wasfound that only samples containing an epoxy compound having at least onegroup of formula (AO) and a compound of formula (IV) in combinationcause scarcely any fluctuation in gradation (Δgamma) before and afterrunning and are excellent in the preservability of image in developedyellow color area.

It will be understood that according to the present invention, there canbe obtained a silver halide color photographic material which has goodyellow color developability and is excellent-in fastness to light. Itwill be further understood that according to the present invention therecan be obtained a silver halide color photographic material which causesscarcely any fluctuation in gradation even when running-processed andwhich gives a dye image excellent in preservability after processing.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide color photographic materialcomprising a support having thereon a yellow color forming silver halideemulsion layer, a magenta color forming silver halide emulsion layer anda cyan color forming silver halide emulsion layer, wherein said yellowcolor forming emulsion layer contains, (i) at least one high silverchloride emulsion having a silver chloride content of not less than 90mol %, (ii) at least one yellow coupler represented by the followinggeneral formula (I) and (iii) at least one compound represented by thefollowing general formula (II), and wherein one or more layers of thephotographic material contains at least one ultraviolet light absorber:

wherein R₁ represents a substituent group; R₂ represents a halogen atom,an alkyl group, an aryl group, an alkoxy group, an aryloxy group, adialkylamino group, an alkylthio group or an arylthio group; R₃represents a group which can be attached to the benzene ring; X₁represents a hydrogen atom or a group which can be eliminated by acoupling reaction with the oxidation product of an aromatic primaryamine developing agent; and p represents an integer of 0 to 4 and when pis 2 or greater, the two or more R3 groups may be the same or different;

wherein R₄, R₅, R₆ and R₇ each represents an alkyl group having 4 to 18carbon atoms and the total number of carbon atoms in R₄, R₅, R₆ and R₇is not more than 32; and X₂ represents a simple bond, an oxygen atom, asulfur atom, a sulfonyl group or a bonding group represented by thefollowing general formula (B):

wherein R₂₁ and R₂₂ each represents a hydrogen atom or an alkyl grouphaving 1 to 10 carbon atoms; and n represents an integer of 1 to 3 andwhen n is 2 or 3, the two or three R₂₁ groups and the two or three R₂₂groups may be the same or different.
 2. The silver halide colorphotographic material as in claim 1, wherein said ultraviolet lightabsorber is a compound having an absorption peak in the range of 330 to400 nm and no absorption peak in the range of 420 to 750 nm.
 3. Thesilver halide color photographic material as in claim 2, wherein saidultraviolet light absorber is represented by the following formula (Va):

wherein R₁₃ to R₁₆ each represents a hydrogen atom, a halogen atom, anitro group, a hydroxyl group, an alkyl group, an alkoxy group, an arylgroup, an aryloxy group, an acylamino group, a carbamoyl group, a sulfogroup, an alkylthio group or an arylthio group, wherein R₁₃ and R₁₄,and/or R₁₅ and R₁₆ may combine to form a ring.
 4. The silver halidecolor photographic material as in claim 2, wherein said ultravioletlight absorber is represented by the following formula (Vb):

wherein R₁₇ and R₁₈ each represents a hydrogen atom, an alkyl group oran acyl group, wherein X₃ represents —CO— or —COO—, and wherein nrepresents an integer of 1 to 4, m represents an integer of 3 to 5, andp represents an integer of 1 to
 4. 5. The silver halide colorphotographic material as in claim 1, wherein said yellow color formingemulsion layer further contains at least one epoxy compound which has atleast one group represented by the following general formula (AO):

wherein R₈, R₉, R₁₀, R₁₁ and R₁₂ may be the same or different and eachrepresents a hydrogen atom, an alkyl group or an aryl group; Rrepresents a substituent group; n represents an integer of 0 to 4; —Y—represents a bivalent bonding group; —X— represents —O—, —S— or —N(R′)—;R′ represents a hydrogen atom, an acyl group, an alkylsulfonyl group, anarylsulfonyl group, an aryl group, a heterocyclic group or—C(R₁₃)(R₁₄)(R₁₅); and R₁₃, R₁₄ and R₁₅ may be the same or different andeach represents an alkyl group or a group represented by the followinggeneral formula (AO-1):

and R₁₃ and R₁₄ each may also represent a hydrogen atom; and when n is 2to 4, the two or more R groups may be the same or different, or any twoof R₈ to R₁₂, R′ and the one R or two R groups may combine to form afive-membered to seven-membered ring, provided that when X is —S—, thetotal number of carbon atoms in the compound is not less than 15; when Xis —O— and Y is —SO₂— or a phenylene, either n is an integer of 1 to 4or at least one of R₈ to R₁₂ is an alkyl group or an aryl group; or whenX is —O— and Y is —O—CO₂—, the total number of carbon atoms in R₈ to R₁₂and the R group or groups is not less than
 10. 6. The silver halidecolor photographic material as in claim 5, wherein said epoxy compoundcontains at least three groups according to general formula (AO).
 7. Thesilver halide color photographic material as in claim 5, wherein saidepoxy compound contains at least four groups according to generalformula (AO).
 8. The silver halide color photographic material as inclaim 5, wherein said epoxy compound contains at least five groupsaccording to general formula (AO).
 9. A silver halide color photographicmaterial comprising a support having thereon a yellow color formingsilver halide emulsion layer, a magenta color forming silver halideemulsion layer and a cyan color forming silver halide emulsion layer,wherein said yellow color forming emulsion layer contains (i) at leastone high silver chloride emulsion having a silver chloride content ofnot less than 90 mol %, (ii) at least one yellow coupler represented bythe following general formula (I):

wherein R₁ represents a substituent group; R₁ in general formula (I)represents a group represented by general formula (D):

wherein R ₃₁ represents a monovalent substituent group excluding ahydrogen atom; and Q represents a nonmetallic atomic group required forforming a three-membered to five-membered hydrocarbon group togetherwith C or a non-metallic atomic group required for forming athree-membered to five-membered heterocyclic ring together with C, saidheterocyclic ring having at least one heteroatom, as a member of thering, selected from the group consisting of N, S, O and P; R₂ representsa halogen atom, an alkyl group, an aryl group, and alkoxy group, anaryloxy group, a dialkylamino group, an alkylthio group or an arylthiogroup; R₃ represents a group which can be attached to the benzene ring,X₁ represents a hydrogen atom or a group which can be eliminated by acoupling reaction with the oxidation product of an aromatic primaryamine developing agent; and p represents an integer of 0 to 4 and when pis 2 or greater, the two or more R₃ groups may be the same or different:, (iii) at least one epoxy compound which has at least one grouprepresented by the following general formula (AO) and which isdifficulty soluble in water:

wherein R₈, R₉, R₁₀, R₁₁ and R₁₂ maybeare the same or different and eachrepresents a hydrogen atom, an alkyl group or an aryl group; Rrepresents a substituent group; n represents an integer of 0 to 4; —Y—represents a bivalent bonding group; —X— represents —O—, —S— or —N(R′)—;R′ represents a hydrogen atom, an acyl group, an alkylsulfonyl group, anarylsulfonyl group, an aryl group, a heterocyclic group or—C(R₁₃)(R₁₄)(R₁₅); and R₁₃, R₁₄ and R₁₅ may be the same or different andeach represents an alkyl group or a group represented by the followinggeneral formula (AO-1):

and R₁₃ and R₁₄ each may also represent a hydrogen atom; and when n is 2to 4, the two or more R groups may be the same or different, or any twoof R₈ to R₁₂, R′ and the one R or two R groups may combine to form afive-membered to seven-membered ring, provided that when X is —S—, thetotal number of carbon atoms in the compound is not less than 15; when Xis —O— and Y is —SO₂— or a phenylene, either n is an integer of 1 to 4or at least one of R₈ to R₁₂ is an alkyl group or an aryl group; or whenX is —O— and Y is —O—CO₂—, the total number of carbon atoms in R₈ to R₁₂and the R group or groups is not less than 10; and (iv) at least onecompound represented by the following general formula (IV):

wherein R₁, R₂, R₃ and R₄ in general formula (IV) independentlyrepresent a hydrogen atom, an aliphatic group, an aromatic group, analiphatic oxycarbonyl group, an aromatic oxycarbonyl group or acarbamoyl group with the proviso that all of R₁, R₂, R₃ and R₄ are notsimultaneously a hydrogen atom; the total number of carbon atoms in R₁to R₄ is 8 to 60; and R₁ and R₂ or R₃ and R₄ may combine to form afive-membered to seven-membered ring.
 10. The silver halide colorphotographic material as in claim 1, wherein R₁ in the above definedgeneral formula (I) represents an aryl group, a tert-alkyl group or agroup represented by the following general formula (D):

wherein R₃₁ represents a monovalent substituent group excluding ahydrogen atom; and Q represents a nonmetallic atomic group required forforming a three-membered to five-membered hydrocarbon group togetherwith C or a non-metallic atomic group required for forming athree-membered to five-membered heterocyclic ring together with C, saidheterocyclic ring having at least one heteroatom, as a member of thering, selected from the group consisting of N, S, O and P.
 11. Thesilver halide color photographic material as in claim 1, wherein R₁ ingeneral formula (I) represents a group represented by general formula(D):

wherein R₃₁ represents a monovalent substituent group excluding ahydrogen atom; and Q represents a non-metallic atomic group required forforming a three-membered to five-membered hydrocarbon group togetherwith C or a non-metallic atomic group required for forming athree-membered to five-membered heterocyclic ring together with C, saidheterocyclic ring having at least one heteroatom, as a member of thering selected from the group consisting of N, S, O and P.
 12. The silverhalide color photographic material as in claim 9, wherein R₁ in generalformula (I) represents an aryl group, a tert-alkyl group or a grouprepresented by general formula (D):

wherein R₃₁ represents a monovalent substituent group excluding ahydrogen atom; and Q represents a non-metallic atomic group required forforming a three-membered to five-membered hydrocarbon group togetherwith C or a non-metallic atomic group required for forming athree-membered to five-membered heterocyclic ring together with C, saidheterocyclic ring having at least one heteroatom, as a member of thering, selected from the group consisting of N, S, O and P.
 13. Thesilver halide color photographic material as in claim 9, wherein R₁ ingeneral formula (I) represents a group represented by general formula(D):

wherein R₃₁ represents a monovalent substituent group excluding ahydrogen atom; and Q represents a non-metallic atomic group required forforming a three-membered to five-membered hydrocarbon group togetherwith C or a non-metallic atomic group required for forming athree-membered to five-membered heterocyclic ring together with C, sadheterocyclic ring having at least one heteroatom, as a member of thering, selected from the group consisting of N, S, O and P.
 14. Thesilver halide color photographic material as in claim 5, wherein saidepoxy compound having at least one group represented by general formula(AO) contains at least two benzene rings.
 15. The silver halide colorphotographic material as in claim 5, wherein said epoxy compound havingat least one group represented by general formula (AO) contains at leastthree benzene rings.
 16. The silver halide color photographic materialas in claim 5, wherein said epoxy compound having at least one grouprepresented by general formula (AO) contains at least four benzenerings.
 17. The silver halide color photographic material as in claim 9,wherein said epoxy compound having at least one group represented bygeneral formula (AO) contains at least two benzene rings.
 18. The silverhalide color photographic material as in claim 9, wherein said epoxycompound having at least one group represented by general formula (AO)contains at least three benzene rings.
 19. The silver halide colorphotographic material as in claim 9, wherein said epoxy compound havingat least one group represented by general formula (AO) contains at leastfour benzene rings.
 20. The silver halide color photographic material asin claim 1, wherein said ultraviolet light absorber is added to a silverhalide emulsion layer which is the farthest of any emulsion layer fromthe support.